CN108950349A - A kind of CoFeNi2VZrx eutectic high-entropy alloy and preparation method thereof - Google Patents
A kind of CoFeNi2VZrx eutectic high-entropy alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of CoFeNi2VZrx eutectic high-entropy alloy, component Co, Fe, Ni, V, Zr content are 1:1:2:1:x according to molar ratio computing, wherein x=0.5~0.6 (molar ratio).Solve the problems, such as that intensity present in existing alloy and plasticity do not coexist, which possesses by the microstructure of FCC solid solution and hard intermetallic compound two-phase eutectic, reaches the balance of plasticity and intensity.It is another object of the invention to provide the CoFeNi2The preparation method of VZrx eutectic high-entropy alloy.The invention also discloses a kind of CoFeNi2The preparation method of VZrx eutectic high-entropy alloy, is specifically implemented according to the following steps: step 1, carrying out pre-treatment to raw material；Step 2, raw material is weighed according to the ratio that molar ratio is 1:1:2:1:0.5~0.6；Step 3, melting.
Description
Technical field
The invention belongs to eutectic high-entropy alloy and its preparation technical fields, are related to a kind of CoFeNi2The high entropy of VZrx eutectic closes
Gold, the invention further relates to the CoFeNi2VZrx eutectic high-entropy alloy and preparation method thereof.
Background technique
High-entropy alloy is considered as one of three quantum jumps of alloying theory in recent decades, it has broken conventional alloys
Design Thinking: use five kinds or five kinds or more of element by equimolar than or nearly equimolar ratio in the form of design alloy,
And the content of each element controls between 5%~35%, the high entropy solid solution alloy that this forms it is in wear-resistant material, hard
There is potential using value in terms of alloy and high temperature alloy.
With the deep progress of research, largely research shows that in the prevalence of such rule in high-entropy alloy: single
The high-entropy alloy of mutually soft FCC configuration has good plasticity and intensity is insufficient, single-phase hard BCC structure or contains hard phase
The high-entropy alloy of intermetallic compound has higher intensity and plasticity is poor, if alloy can possess FCC and BCC or hard
Intermetallic compound double structure, then the balance of plasticity and intensity can be reached.Dalian University of Technology's Patent No.
A kind of CoFe of the patented invention of (201710891492.1 CN107557643A)xNiyV0.5NbzHigh-entropy alloy, in patent
CoFeNi2V0.5Nb0.75High-entropy alloy possesses FCC and Fe2Nb two-phase microstructure, obtains high rigidity and good wearability,
However it cannot be intensity and the good combination of plasticity.
Document (L.Jiang, Z.Q.Cao, J.C.Jie, J.J.Zhang, Y.P.Lu, T.M.Wang, T.J.Li, Effect
of Mo and Ni elements on microstructure evolution and mechanical properties
of the CoFeNixVMoy high entropy alloys,Journal of Alloys and Compounds 649
(2015) 585-590) in report CoFeNiVMo0.6And CoFeNi1.4VMo eutectic high-entropy alloy, have it is higher surrender and
Breaking strength (close to 2000MPa), however almost without plastic deformation (compression deformation is less than 5%), still do not solve
The problem of plasticity present in high-entropy alloy and intensity can be good and be deposited.
Summary of the invention
The present invention provides a kind of CoFeNi2VZrx eutectic high-entropy alloy, solve intensity present in existing alloy and
The problem of plasticity does not coexist, the alloy possess by the microstructure of FCC solid solution and hard intermetallic compound two-phase eutectic, reach
To the balance of plasticity and intensity.
The technical scheme adopted by the invention is that a kind of CoFeNi2VZrx eutectic high-entropy alloy, component Co, Fe,
Ni, V, Zr content are 1:1:2:1:x according to molar ratio computing, wherein x=0.5~0.6 (molar ratio).
It is another object of the invention to provide the CoFeNi2The preparation method of VZrx eutectic high-entropy alloy.
Another technical solution of the invention is a kind of CoFeNi2The preparation method of VZrx eutectic high-entropy alloy, specifically according to
Following steps are implemented:
Step 1, pre-treatment is carried out to raw material；
Step 2, raw material Co, Fe, Ni, V and Zr elemental gold is weighed according to the ratio that molar ratio is 1:1:2:1:0.5~0.6
Belong to；
Step 3, melting prepares CoFeNi2VZrx eutectic high-entropy alloy.
The features of the present invention also characterized in that
Step 1 specific method is to polish Co block, Fe stick, Ni block, and be respectively placed in different beakers
In, in addition V piece and Zr stick are respectively placed in different beakers.Then, then a certain amount of alcohol is poured into, ultrasonic cleaning 15~
20 minutes, to remove the oxide skin and impurity on raw material surface.Then the raw material after cleaning is dried up again with hair dryer, is handled
Clean Co, Fe, Ni, V and Zr raw material.
The step 2 specifically, high-purity Co block, Fe stick, Ni block, V piece and Zr stick purity be not less than 99.9wt%.
The step 3 method particularly includes:
Step 3.1, the raw metal to melting weighed in step 2 is successively put from the bottom up from low to high according to fusing point
Enter in water jacketed copper crucible, electric arc furnaces working chamber is evacuated to 7.0 × 10-3Pa~5.0 × 10-3Pa, then it is passed through high-purity argon gas work
For protective gas, argon pressure in furnace is made to reach 0.05~0.06MPa；
Step 3.2, start electric arc melting, fusion current is 420~470A, and object to be mixed all melts, and opens electromagnetism and stirs
It mixes, stirring required electric current is 12~14A, and after keeping 8~10min, cooled alloy liquid obtains first ingot casting.
Step 3.3, ingot casting is overturn by manipulator in crucible, then starts melting again, fusion current is
420~470A opens electromagnetic agitation to whole fusings, and electric current needed for stirring is 12~14A, cooling to close after keeping 8~10min
Golden liquid obtains second of ingot casting；
Step 3.4, it repeats step 3.3 three times, finally obtains the uniform CoFeNi of structural constituent2VZrx eutectic high-entropy alloy
Ingot casting.
The invention has the advantages that CoFeNi prepared by the present invention2VZrx eutectic high-entropy alloy, tissue are solid for FCC
Solution and hard intermetallic compound two-phase eutectic, by its plasticity of active balance and intensity.Wherein, the addition of zirconium produces alloy
The utility model has the advantages that first, element Zr are that atomic radius is maximum in five elements below rawThe addition of element, Zr will lead to alloy
It is middle to generate strong distortion of lattice, improve the hardness and strength of alloy.Second, usual FCC solid solution others BCC or HCP relatively
Structure mutually has better plasticity, thus plasticity and intensity can reach good balance.
The CoFeNi that XRD spectrum of the invention is prepared with embodiment 12VZr0.55For eutectic high-entropy alloy, alloy is by FCC
Phase (CoFeNiV phase: Co:20.00, Fe:24.29, Ni:28.45, V:27.26 (at.%)) and intermetallic compound Ni7Zr2
(Ni:50.07, Zr:19.21, Co:14.13, Fe:11.84, V:4.75 (at.%)) composition, as shown in Figure 1.
Detailed description of the invention
Fig. 1 is CoFeNi prepared by the embodiment of the present invention 12VZr0.55The XRD diagram of eutectic high-entropy alloy；
Fig. 2 is CoFeNi prepared by the embodiment of the present invention 12VZr0.55The SEM of eutectic high-entropy alloy schemes；
Fig. 3 is CoFeNi prepared by the embodiment of the present invention 22VZr0.5The SEM of eutectic high-entropy alloy schemes；
Fig. 4 is CoFeNi prepared by the embodiment of the present invention 32VZr0.6The SEM of eutectic high-entropy alloy schemes.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of CoFeNi of the present invention2VZrx eutectic high-entropy alloy, component Co, Fe, Ni, V, Zr content according to mole
Than being calculated as 1:1:2:1:x, wherein x=0.5~0.6 (molar ratio).
The present invention provides a kind of CoFeNi2The preparation method of VZrx eutectic high-entropy alloy, it is specifically real according to the following steps
It applies:
Step 1, pre-treatment is carried out to raw material；
Specific method is to polish Co block, Fe stick, Ni block, and be respectively placed in different beakers, in addition by V piece
It is respectively placed in Zr stick in different beakers.Then, then a certain amount of alcohol is poured into, ultrasonic cleaning 15~20 minutes, to go
Except the oxide skin and impurity on raw material surface.Then the raw material after cleaning is dried up with hair dryer again, obtain handling clean Co,
Fe, Ni, V and Zr raw material.
Step 2, raw material Co, Fe, Ni, V and Zr elemental gold is weighed according to the ratio that molar ratio is 1:1:2:1:0.5~0.6
Belong to；High-purity Co block, Fe stick, Ni block, V piece and Zr stick purity be not less than 99.9wt%.
Step 3, melting prepares CoFeNi2VZrx eutectic high-entropy alloy, is specifically implemented according to the following steps:
Step 3.1, the raw metal to melting weighed in step 2 is successively put from the bottom up from low to high according to fusing point
Enter in water jacketed copper crucible, electric arc furnaces working chamber is evacuated to 7.0 × 10-3Pa~5.0 × 10-3Pa, then it is passed through high-purity argon gas work
For protective gas, argon pressure in furnace is made to reach 0.05~0.06MPa；
Step 3.2, start electric arc melting, fusion current is 420~470A, and object to be mixed all melts, and opens electromagnetism and stirs
It mixes, stirring required electric current is 12~14A, and after keeping 8~10min, cooled alloy liquid obtains first ingot casting.
Step 3.3, ingot casting is overturn by manipulator in crucible, then starts melting again, fusion current is
420~470A opens electromagnetic agitation to whole fusings, and electric current needed for stirring is 12~14A, cooling to close after keeping 8~10min
Golden liquid obtains second of ingot casting；
Step 3.4, it repeats step 3.3 three times, finally obtains the uniform CoFeNi of structural constituent2VZrx eutectic high-entropy alloy
Ingot casting.
Embodiment 1
A kind of CoFeNi2VZr0.55Eutectic high-entropy alloy, component Co, Fe, Ni, V, Zr content is according to molar ratio computing
For 1:1:2:1:0.55, prepared especially by the following method:
Step 1, pre-treatment is carried out to raw material；
Specific method is to polish Co block, Fe stick, Ni block, and be respectively placed in different beakers, in addition by V piece
It is respectively placed in Zr stick in different beakers.Then, then a certain amount of alcohol is poured into, ultrasonic cleaning 15 minutes, to remove original
Expect the oxide skin and impurity on surface.Then the raw material after cleaning is dried up with hair dryer again, obtain handling clean Co, Fe, Ni,
V and Zr raw material.
Step 2, raw material Co, Fe, Ni, V and Zr elemental metals are weighed according to the ratio that molar ratio is 1:1:2:1:0.55；Institute
The purity of high-purity Co block, Fe stick, Ni block, V piece and the Zr stick stated is not less than 99.9wt%.
Step 3, melting prepares CoFeNi2VZr0.55Eutectic high-entropy alloy, is specifically implemented according to the following steps:
Step 3.1, the raw metal to melting weighed in step 2 is successively put from the bottom up from low to high according to fusing point
Enter in water jacketed copper crucible, electric arc furnaces working chamber is evacuated to 7.0 × 10-3Pa, then high-purity argon gas is passed through as protective gas, make
Argon pressure reaches 0.05MPa in furnace；
Step 3.2, start electric arc melting, fusion current 420A, object to be mixed all melts, opens electromagnetic agitation, stir
Mixing required electric current is 14A, and after keeping 10min, cooled alloy liquid obtains first ingot casting.
Step 3.3, ingot casting is overturn by manipulator in crucible, then starts melting again, fusion current is
420A opens electromagnetic agitation to whole fusings, and electric current needed for stirring is 14A, and after keeping 10min, cooled alloy liquid obtains the
Secondary ingot casting；
Step 3.4, it repeats step 3.3 three times, finally obtains the uniform CoFeNi of structural constituent2VZr0.55The high entropy of eutectic closes
The ingot casting of gold.
Fig. 2 is CoFeNi prepared by embodiment 12.0VZr0.55The scanning electron microscope organization chart (SEM figure) of high-entropy alloy, Fig. 2
It (a) is the microstructure under low power, Fig. 2 (b) is the microstructure in Fig. 2 (a) under the high power of corresponding region.It can from figure
Out, alloy structure is by black FCC phase and white Ni7Zr2Phase two-phase eutectic composition, wherein eutectic structure includes coarse Eutectic Layer
Piece, tiny eutectic lamellar and divorsed eutectic, this illustrates CoFeNi2VZr0.55High-entropy alloy is a kind of organizes as Eutectic Morphology
CoFeNi is prepared in alloy2VZr0.55Eutectic high-entropy alloy.
Embodiment 2
A kind of CoFeNi2VZr0.5Eutectic high-entropy alloy, component Co, Fe, Ni, V, Zr content is according to molar ratio computing
For 1:1:2:1:0.5, prepared especially by the following method:
Step 1, pre-treatment is carried out to raw material；
Specific method is to polish Co block, Fe stick, Ni block, and be respectively placed in different beakers, in addition by V piece
It is respectively placed in Zr stick in different beakers.Then, then a certain amount of alcohol is poured into, ultrasonic cleaning 17 minutes, to remove original
Expect the oxide skin and impurity on surface.Then the raw material after cleaning is dried up with hair dryer again, obtain handling clean Co, Fe, Ni,
V and Zr raw material.
Step 2, raw material Co, Fe, Ni, V and Zr elemental metals are weighed according to the ratio that molar ratio is 1:1:2:1:0.5；Institute
The purity of high-purity Co block, Fe stick, Ni block, V piece and the Zr stick stated is not less than 99.9wt%.
Step 3, melting prepares CoFeNi2VZr0.5Eutectic high-entropy alloy, is specifically implemented according to the following steps:
Step 3.1, the raw metal to melting weighed in step 2 is successively put from the bottom up from low to high according to fusing point
Enter in water jacketed copper crucible, electric arc furnaces working chamber is evacuated to 6.0 × 10-3Pa, then high-purity argon gas is passed through as protective gas, make
Argon pressure reaches 0.055MPa in furnace；
Step 3.2, start electric arc melting, fusion current 445A, object to be mixed all melts, opens electromagnetic agitation, stir
Mixing required electric current is 13A, and after keeping 9min, cooled alloy liquid obtains first ingot casting.
Step 3.3, ingot casting is overturn by manipulator in crucible, then starts melting again, fusion current is
445A opens electromagnetic agitation to whole fusings, and electric current needed for stirring is 13A, and after keeping 9min, cooled alloy liquid obtains second
Secondary ingot casting；
Step 3.4, it repeats step 3.3 three times, finally obtains the uniform CoFeNi of structural constituent2VZr0.5The high entropy of eutectic closes
The ingot casting of gold.
Fig. 3 is CoFeNi prepared by embodiment 22VZr0.5The scanning electron microscope organization chart (SEM figure) of high-entropy alloy, Fig. 3 (a)
For the microstructure under low power, Fig. 3 (b) is the microstructure in Fig. 3 (a) under the high power of corresponding region.It can be seen from the figure that closing
Payment organization is by black FCC phase and white Ni7Zr2Phase two-phase eutectic composition, wherein eutectic structure include thicker eutectic lamellar, it is thin
Small or superfine small eutectic lamellar, netted eutectic and divorsed eutectic, this illustrates CoFeNi2VZr0.5High-entropy alloy is a kind of tissue
For the alloy of Eutectic Morphology, that is, CoFeNi is prepared2VZr0.5Eutectic high-entropy alloy.
Embodiment 3
A kind of CoFeNi2VZr0.6Eutectic high-entropy alloy, component Co, Fe, Ni, V, Zr content is according to molar ratio computing
For 1:1:2:1:0.6, prepared especially by the following method:
Step 1, pre-treatment is carried out to raw material；
Specific method is to polish Co block, Fe stick, Ni block, and be respectively placed in different beakers, in addition by V piece
It is respectively placed in Zr stick in different beakers.Then, then a certain amount of alcohol is poured into, ultrasonic cleaning 20 minutes, to remove original
Expect the oxide skin and impurity on surface.Then the raw material after cleaning is dried up with hair dryer again, obtain handling clean Co, Fe, Ni,
V and Zr raw material.
Step 2, raw material Co, Fe, Ni, V and Zr elemental metals are weighed according to the ratio that molar ratio is 1:1:2:1:0.6；Institute
The purity of high-purity Co block, Fe stick, Ni block, V piece and the Zr stick stated is not less than 99.9wt%.
Step 3, melting prepares CoFeNi2VZr0.6Eutectic high-entropy alloy, is specifically implemented according to the following steps:
Step 3.1, the raw metal to melting weighed in step 2 is successively put from the bottom up from low to high according to fusing point
Enter in water jacketed copper crucible, electric arc furnaces working chamber is evacuated to 5.0 × 10-3Pa, then high-purity argon gas is passed through as protective gas, make
Argon pressure reaches 0.06MPa in furnace；
Step 3.2, start electric arc melting, fusion current 470A, object to be mixed all melts, opens electromagnetic agitation, stir
Mixing required electric current is 12A, and after keeping 8min, cooled alloy liquid obtains first ingot casting.
Step 3.3, ingot casting is overturn by manipulator in crucible, then starts melting again, fusion current is
470A opens electromagnetic agitation to whole fusings, and electric current needed for stirring is 12A, and after keeping 8min, cooled alloy liquid obtains second
Secondary ingot casting；
Step 3.4, it repeats step 3.3 three times, finally obtains the uniform CoFeNi of structural constituent2VZr0.6The high entropy of eutectic closes
The ingot casting of gold.
Fig. 4 is CoFeNi prepared by embodiment 32VZr0.6The scanning electron microscope organization chart (SEM figure) of high-entropy alloy, Fig. 4 (a)
For the microstructure under low power, Fig. 4 (b) is the microstructure in Fig. 4 (a) under the high power of corresponding region.It can be seen from the figure that closing
Payment organization is by black FCC phase and white Ni7Zr2Phase two-phase eutectic composition, wherein eutectic structure include coarse eutectic lamellar, it is thin
Small or superfine small eutectic lamellar and divorsed eutectic, this illustrates CoFeNi2VZr0.6High-entropy alloy is a kind of organizes as eutectic shape
The alloy of looks, that is, be prepared CoFeNi2VZr0.6Eutectic high-entropy alloy.
Claims (5)
1. a kind of CoFeNi2VZrx eutectic high-entropy alloy, which is characterized in that its component Co, Fe, Ni, V, Zr content are according to rubbing
You are calculated as 1:1:2:1:x by ratio, wherein x=0.5~0.6.
2. a kind of CoFeNi2The preparation method of VZrx eutectic high-entropy alloy, which is characterized in that be specifically implemented according to the following steps:
Step 1, pre-treatment is carried out to raw material；
Step 2, raw material Co, Fe, Ni, V and Zr elemental metals are weighed according to the ratio that molar ratio is 1:1:2:1:0.5~0.6；
Step 3, melting prepares CoFeNi2VZrx eutectic high-entropy alloy.
3. CoFeNi according to claim 22The preparation method of VZrx eutectic high-entropy alloy, which is characterized in that the step
Rapid 1 specifically: polish Co block, Fe stick, Ni block, and be respectively placed in different beakers, in addition distinguish V piece and Zr stick
It is placed in different beakers.Then, then a certain amount of alcohol is poured into, ultrasonic cleaning 15~20 minutes, to remove raw material surface
Oxide skin and impurity.Then the raw material after cleaning is dried up again with hair dryer, obtains handling clean Co, Fe, Ni, V and Zr
Raw material.
4. CoFeNi according to claim 22The preparation method of VZrx eutectic high-entropy alloy, which is characterized in that the step
In rapid 2, high-purity Co block, Fe stick, Ni block, V piece and Zr stick purity be not less than 99.9wt%.
5. CoFeNi according to claim 22The preparation method of VZrx eutectic high-entropy alloy, which is characterized in that the step
Rapid 3 specifically,
Step 3.1, the raw metal to melting weighed in step 2 is sequentially placed into water according to fusing point from the bottom up from low to high
In cold copper crucible, electric arc furnaces working chamber is evacuated to 7.0 × 10-3Pa~5.0 × 10-3Pa, then high-purity argon gas is passed through as guarantor
Gas is protected, argon pressure in furnace is made to reach 0.05~0.06MPa；
Step 3.2, start electric arc melting, fusion current is 420~470A, and object to be mixed all melts, and opens electromagnetic agitation, stirs
Mixing required electric current is 12~14A, and after keeping 8~10min, cooled alloy liquid obtains first ingot casting.
Step 3.3, ingot casting being overturn by manipulator in crucible, then starts melting again, fusion current is 420~
470A opens electromagnetic agitation to whole fusings, and electric current needed for stirring is 12~14A, after keeping 8~10min, cooled alloy liquid,
Obtain second of ingot casting；
Step 3.4, it repeats step 3.3 three times, finally obtains the uniform CoFeNi of structural constituent2The casting of VZrx eutectic high-entropy alloy
Ingot.
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| CN113798495A (en) * | 2021-08-12 | 2021-12-17 | 西安理工大学 | High-entropy alloy sintering forming process with double-element equivalent transformation |
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| CN114836669B (en) * | 2022-05-18 | 2023-01-31 | 中国科学院兰州化学物理研究所 | Co-Fe-Ni-V-Zr eutectic high-entropy alloy and preparation method thereof |
| CN115233070A (en) * | 2022-06-22 | 2022-10-25 | 大连理工大学 | High-entropy alloy with double-phase eutectic structure and preparation method thereof |
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